Long chain alkyl acetophenone-alpha-sulfonic acids and salts



Patented May 22, 1951 LONG CHAIN ALKYL ACETOPHENONE-a- SULFONIC ACIDS AND SALTS Franklin ML Watkins, Flossmoor, 111., assignor to Sinclair Refining Company, New York, N. Y., a corporation of Maine No Drawing.

Original application September 16,

1947, Serial No. 774,431. Divided and this application March 4, 1949, Serial No. 79,735

4 Claims. 1

My invention relates to new surface-active compounds useful as wetting, cleansing and. dispersing agents.

My compounds are metal sulfo-derivatives of alkylated acetophenone and conform to the formula,

in which R is an alkylated aryl group comprising an alkyl radical containing from to 26 carbon atoms, nis 1 or 2, and M an alkali or alkaline earth metal. As exemplary of the compounds may be mentioned, the sodium, potassium, calcium, barium, and magnesium sulfonates of laurylacetophenone, t e t r a d e c yl a c etophenone, hexadecylac-etophenone, heptadecylaoetophenone, octadecylacetophenone, docosanylacetophenone, and the like.

The compounds are characterized, inter alia, in that they are soluble to a more than appreciable extent in mineral oils. It is my belief that this oil solubility obtains by reason of the sulfo group being positioned alpha with reference to the carbonyl group which allows of chelation between the metal and the carbonyl oxygen, but, of course, I am not to be held for the accuracy of this hypothesis. The oil solubility of the compounds is such as to permit of their use as detergents and dispersants in mineral lubricating oils. This is not true of most of the presently commercially available synthetic sulfonates of related chemical structure. Thus, whereas the alpha-sodium sulfonate of p-octadecylacetophenone, one of the preferred compounds of my invention, is soluble in mineral lubricating oils to the extent of 6% or more, the sodium sulfonates of methyl esters of high molecular weight fatt acids, the alphasodium sulfonate of methyl palmitate, for example, possess no appreciable solubility in such oils.

The compounds may be prepared by several different procedures. Generally, I prepare the sodium-containing compounds by reacting sodium sulphite, in the presence of a suitable solvent, with compounds of the formula RCOCHZX, where R has the same significance as above and X represents halogen. The calcium or bariumcontaining compounds may be conveniently produced metathetically from the sodium-containing compounds by reacting the latter with salts of the alkaline earth metals, most suitably the chlorides or bromides.

The new compounds are particularly useful in mineral lubricating compositions, and this application represents a division of my copending application Serial No. 774,431, filed September 16,

1947, now Patent Number 2,529,424, which discloses and claims such compositions, In preparing the lubricating composition 1' may add the metal sulfo-compound in any amount effective to impart a detergent property to the base oil, but the limit of solubility of the compound in the base oil, of course, should not be exceeded. Generally, the composition is prepared to contain from 0.25 to 2.0% on the weight of the oil of the metal sulfo-compound.

Addends other than the metal sulfo-compound may be present in the lubricating composition. Thus, there may be present a rust-inhibitor, for example, or a viscosit index improver or pour depressor, or an anti-oxidant, such as a phosphorus sulfide-turpentine reaction product.

My invention is illustrated by the following examples which are not to be taken as in any way restrictive of the scope of the invention:

EXAMPLE I To about 0.14 mole of crude p-octadecylphenacyl bromide, produced by the bromination of acetylated oetadecylbenzene, was added 53 grams (0.42 mole) of sodium sulphite in 400 cc. of an alcohol in water solution containing 30 volume percent alcohol. The mixture was refluxed With stirring for 9 hours, some of the solvent being allowed to distill off. The solvent was then evaporated to leave a brown solid which was taken up in benzol, filtered clear, and obtained again by evaporation of the benzol. Forty-two grams of product was obtained, analyzing 4.12% sodium as against 4.85 theoretical for the alpha-sodium sulfonate of p-octadecylacetophenone, -a--purity of about EXALEPLE II The alpha-sodium sulfonate of p-laurylacetophenone was prepared as follows: To a 1 gallon autoclave were charged 563 grams (1.52 mols.) of crude alpha-chloro-p-laurylacetophenone, 441 grams (3.5 mols.) of anhydrous sodium sulfite, 1500 cc. of water, 750 cc. of alcohol, and 1000 cc. of xylene. The reaction mixture was stirred and heated at 300 F. for .15'. hours'atapressure of p. s. i. gauge,- and thenremoved from the autoclave and filtered. Some solid material at the bottom of the autoclave was discarded.

The organic layer of the filtrate was charged to a 3-liter, three-neck flask fitted with a water trap and a reflux condenser and refluxed until the water and alcohol were removed. The xylene solution was filtered and topped under plant vacuum to 360 F. bottom temperature giving 487 product was obtained. chiefly of the desired alpha-calcium sulfonate of grams of a soft red-brown solid containing 7.25% sodium, 0.36% chlorine, and 6.50% sulfur.

EXAMPLE III Four hundred and fifty-eight grams '(1.45:mols. based on theso'dium content) of alpha-sodium sulfonate of p-laurylacetophenone was dissolved in 1 liter of xylene and the solution heated'to 190 F. Ninety-two and two-tenths .--grams .of calcium chloride (155% of theoretica1):in. a20% aqueous solution was added dropwise to the xylene solution, the temperature dropping to 170 The mixture was stirred at 170"F.'f0r 2 hours before being allowed to settle overnight.

The aqueous layer was drawn (off and 1 92.2 grams of calcium chloride-ina 20%iaqueouszso'lution was added to the xylene layerat-room'temperature following which the mixture Washeated, with stirring, to 220 F. in 2 hours. It was necessary to add more xylene from time to time as the "mixture emulsified and became rather viscous. The emulsion was broken by heat and the water drawn off.

The xylenesolution was heated to 150 108 grams of calcium hydroxide and 75cc. of water added, and the mixture stirred at 150-180" F. for

2hours. "It was then-heated to 280 F. and held at that temperature for 15 minutesbefore'it was 'filteredan'd topped under plant vacuum'to 330 F. bottom temperature. A- yield 'of 306 grams of The product, consisting p-laurylacetophenone, contained 5.28% calcium,

5.38% sulfur, 0.68% chlorine, 0.08% sodium, and had an acid number of 9.5.

EXAMPLE IV .qualities of 'theproduct. The test used isthat identified inthe art as the Ir-4 Chevrolet Engine Test.

which the results of the test are apparent, the

As indicated in the table below from .blend contained1.4% of the additive.

Table Alpha- Base Oil Calcium Free of Sulfonate Metal of p-lauryl- Sulioacetophecompound none Blend Composition, weight percent Base Oil 97.10 Alpha-calcium sulfonate of p-laiuylacetophenone 1.40 Corrosion Inhibitor 1.00 .rPourlD epressor 50 --Anti-foam Agent 0 0005 0 0005 ILaboratory' Tests Gravity 30. 5 29. 9 1 Flash 395 .400 .Fire 450 450 V s. ac,100. 156 163. 2 v1s. at 210.-.. 43. 3 44. s Viscosity: Index 92. 8 107 Pour 15 Calcium; percent 0.079 v Sodlum; percentlhosphorus, perce 0. 082 Sulfur, percent 0. 2 .0. 32

Table-Continued Alpha- Base Oil Calcium Freeof sulfonate Metal of p-lau- Sulforylacetocompound phenone Blend L.4 Ratings Varnish Rating:

Piston Skirts .1 3.0 5.0 Rocker Arm Cover Plat 8.0 9.0 Push .Rod Cover. Plate 8. 5 8.0 Cylinder'Walls 3- 0 5. 0 "Cra'nkcase Oil Pan 0. 0 9. 0

Varnishflotal 28. 5 3G. 0

" Sludge Rating:

Rocker Arm-Assembly 6. 0 9.0 Rocker Arm Cover Plate" 5. 5 9.0 :PuslTRod Cover Plate 5.0 9. 0 Oil Screen r. 7.0 9. 5 Crankcasc Oil Pan 7. 5 9.0

Sludge Total 31. 0 45. 5

Total Varnish and Sludge Rating 59. 5 ,81. 5 Bearing Loss (Mg/Whole) 1,300 557 "Used Oil Testsat 36llrs.:

Vis.-. Rise at 100. F., percent 64. 7 .58. 7 Acid N0 3. 20 2.

From this table itiis to .be particularly noted that the total varnish and sludge rating was ma- .teri'ally higher in the: case of the blend. and that thebearing loss was moreithan halved. .Therhigh varnish-sludge rating, of course, demonstrates the detergent properties of the additive.

.I claim:

1. A compound of the formula in which R. is a substituted phenyl group having as the sole benzene ring substituent one alkyl Jradicalcontaining from 10 to 26. carbon atoms, n "is 1 or'2, and .M an alkali or alkaline earth metal.

- 2.'The alpha-sodium sulfonate of p-octadecylr acetophenone.

3. The alpha-sodium sulfonate of p-laurylacetophenone.

4. The alpha-calcium sulfonate of p'-laurylacetophenone.

FRANKLIN. M. WATKINS.

REFERENCES CITED :The following references are of record in the lfile of this patent:

UNITED STATES PATENTS Number Name Date ..2,086,216 De Groote .July 6, 1937 2,089,154 Ralston Aug..3, 1937 2,291,778 Wakeman Aug. 4, 1942 OTHER REFERENCES 

1. A COMPOUND OF THE FORMULA 